Certain new heterocyclic compounds and method of making same



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CERTAIN NEW HETEROCYCLIC COMPOUNDS AND METHOD OF MAKING SAME Verner L. Stromberg, Shrewsbury, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application December 30, 1954, Serial No. 478,933

Claims. (Cl. 260211) Or the hydrogenated derivatives thereof, such as:

In the above structures the radical RC is the residual radical derived from a monocarboxy acid RCOOH. Such acid may have one carbon atom as in the case of formic acid or may have only 2 carbon atoms as in the case case of acetic acid, or may have as many as 30 carbon atoms as in the case of a higher fatty acid.

The above formulas show the compounds derived from a substituted imidazoline, i. e., a five-membered ring compound but it is to be noted that comparable compounds having a six-membered ring are included. Such compounds instead of being derivatives of substituted imidazolines are derivatives of substituted tetrahydropyrimidines. course, belong to the broader class of cyclic amidines.

The compounds above depicted are derivatives of triamine but one can use derivatives of higher alkylene amines such as triethylene tetramine, tetraethylene pentamine, etc. In such instances the secondary divalent amino radical, such as would appear in the radical which links the heterocyclic ring With the hexose residue.

The type of compound herein depicted is not limited to monocarboxy acids, such as acetic acid and higher fatty acids, but includes dicarboxy acids such as diglycolic acid, dimeric fatty acids obtained by the .di-

merization of unsaturated higher fatty acids such as" linseed oil fatty acid, etc.

-More specifically then the herein described amidines may be exemplified by' the formula:

/N R-C: 12

Both types of cyclic compounds, of

2,792,390 Patented May 14,

2 in which has its previous significance, and R is a member of the class consisting of H H HOH HOE in which R" is a radical selected from the class consisting of RNHz or H (R'N),.H in which R has its prior significance and n is a small whole number. The amino cyclic amidine above depicted is combined with a hexose such as glucose.

If, however, the cyclic amidine is derived from a dicarboxy acid, such as HOOO-R1-COOH in which R1 is the carboxyl-free dicarboxy' acid residue, the dicyclic amidine obtained would correspond to in which the various characters have their prior significance.

In recapitulation then, the present invention is concerned with certain Schifls Bases and hydrogenated derivatives thereof. The Schiffs Bases are obtained by reaction between:

(A) A member of the class consisting of:

(a) Substituted imidazolines and substituted tetrahydropyrimidines thereof, characterized by the presence of a terminal primary amino group, and

(b) Substituted diimidazolines and substituted ditetrahydropyrimidines, characterized by the presence of a 2 terminal primary amino group, and

(B) At least one mole of a hydroxylated aldehyde such as a hexose and particularly as exemplified by glucose.

In the case of the dicyclic compounds, reaction may involve one mole or 2 moles of glucose.

For convenience, What is said hereinafter will be divided into six parts:

Part 1 is" concerned with suitable cyclic compounds containing a primary amino group in the terminal position. divisions:

Division A is concerned with substituted imidazolines obtained from monocarboxy acids;

Division B is concerned with suitable substituted tetrahydropyrimidines obtained from monocarboxy acids;

Division C is concernedwith substituted imidazolines obtained from dicarboxy acids;

Division D is concerned with substituted tetrahydro pyrimidines I obtained fromdicarboxy' acids;

Part 2 is" concerned with: suitable hexoss or otherpolyols having a reactive aldehydic carbonyl group as exemplified by glucose;

Part 1, for convenience, is divided into four Part 3 is concerned with the reaction involving the first two classes enumerated above;

Part 4 is concerned with hydrogenated derivatives of the compounds described in Part 3, preceding; I

Part 5 is concerned with uses for the products obtained in Parts 3 and 4, preceding, and particularly those in which there is present a radical having at least 8 uninterrupted carbon atoms and preferably showing character: istic surface-activeproperties; and 7 Part 6 is concerned with derivatives obtained from the compounds described in Parts 3 and 4, preceding, in which such compounds serve as an intermediate for further reaction.

PART 1 Division A Substituted imidazolines are obtained from a variety of acids beginning with the one-carbon acid (formic) through and including higher fatty acids or the equivalent having as many as 32 carbon atoms. Modified fatty acids also can be'employed as, for example, phenyl stearic acid or the like. Cyclic acids may be employed, including naphthenic acids. A variety of other acids including benzoic acid, substituted benzoic acid, solicyclic acid, and the like, have been employed to furnish the residue RC from the acid RCOOH in which the C of the residue RC is part of the ring. The fatty acids employed for example, may be saturated or unsaturated. They may be hydroxylated or nonhydroxylated. Branched long chain fatty acids may be employed. See J. Am. Chem. Soc. 74, 2523 (1952). This applies also to the lower molecular weight acids as well.

it will be noted that a variety of substituted imidazolines are included in Table 1 following. In some instances there is a radical having 8 or more uninterrupted carbon atoms and in other instances this is not the case.

Actually, substituted imidazolines can be obtained from a variety of polyamines but only in the instance where one starts with a triamine or higher amine is there a residual group having a primary amino radical as herein required. This does not mean, however, that one could not start with ethylene diamine or with 1,2-propylene diamine. The cyclic compounds so obtained could be reacted with a mole of ethylene imine or propylene imine so as to introduce the terminal primary amino group. From a practical standpoint, however, the most readily available polyamines are diethylene triamine, triethylene tetramine, and tetraethylene pentamine. No particular advantage has been found in using other polyamines in which some other divalent radical, such as appears. For this reason examples in .Table 1 are limited to derivatives of the three most readily available polyamines above indicated.

TABLE 1 N N-R i i Ex. RCOOH Source R No. ofRO Formicnn CHZGHZNHI Pr0pi0nic V CHzCHzNHz Isovalerie CHzCHzNHz stearic. CH2CH2NH2 OHzCHaNHz CH2CH2NH: CHZCHZNHQ CHzCHzNHz CHzCH'zNH: .OHZGHQNHQ CHzCHgNHCHgCHzNHZ CHzCHzNHCH2CH2NH2 CHzCHgNECHzCHzNH; CH3CH2NHCH2CH2NH2 1511-- Cerotic OHzCHzNHCHgOHzNHz 16zz p-tert-Butyl ben- CHzCHzNHCHzCHzNHz zoic. 17a p-Hydroxybenzoic CHgCHzNHCHzCHzNHs l8a Salicylic CHzOHzNHOHzGHzNHs 19a Htyiroxy uaph- CHgCHzNHCHzCHzNHz CH2CH2NHCH2CH2NHZ 21a..- Formic. CH2CH2NHC2HzCHzNHCH2CHzNHz 22m. lVIethyl0ctadeca-' CHzCHzNHC2H2CH2NHCH2CH2NH2 1101c. 231A..- Capric CH2CHzNHCzHsCHzNHCHzCHzNHz 24a. stearic OHZCHRNHC2H2CH2NHCH2OH2NH2 25a Phenylstearic. OH2CH2NHC2H2CH2NHCHzCHzNHz 2611---- Cresotinic CHzCHzNHC2H2CHzNHCH CH2NHz 27a Linoleic CHzOHzNHGzHzCHzNHCHzOHzNHz 28a Salicylic CHzCHzNHCzHgCHzNHCHzCHzNH 29[L 2-Hydr0xy-3- CHzCHzNHCzHzCHzNHCHzCHzNHa methoxyben- 2010. 3011.." Naphthenic CH2CHaNHGzHzOHzNHCHzCHzNH:

The expression detergent-forming acid" has been used a large number of times in various patents to characterize high molal monocarboxy acids having at least 8 and generally not over 32 carbon atoms. Such acids are composed of the elements carbon, hydrogen, and oxygen exclusively. Such acids are obviously characterized, as the name suggests, by the ability to combine with the usual water soluble bases such as caustic soda, caustic potash, ammonia and-1ow molal water-soluble amines, to give water soluble products which are soaps having conventional detersive characteristics in hydrophile systems. They may be obtained not only from the higher fatty acids but also from petroleum sources. This class is illustrated by naphthenic acids and acids obtained by the oxidationof petroleum hydrocarbons. Furthermore, although resin acids such as abietic acid are ordinarily included in the instant invention these are eliminated from the standpoint of cyclic amidine production simply for the reason that ring formation apparently does not take place. They may form salts, however- The normal variants of the fatty acids such as dihydroxy stearic acid and the like are included provided such addition or substitution product does not introduce any new element and provided the compound still has detergent-forming characteristics.

Division B The only polyamine available on a large scale for the manufacture of tetrahydropyrimidines is 3,3-iminobispropylamine. This product can be converted into the tetram'ine or pentamine'by appropriate reaction with a suitable imine or by reaction with acrylonitrile, followed by the usual steps of converting the intermediate into the amine. Tetrahydropyrimidines comparable to the substituted amidines in Tablet, appear in Table 2 immediately following.

TABLE 2 N N-R' Ex. No. RCOOH Source of RC R Formic CHzCHzCHzNH: Acetic CH2CH2CH2NH2 Butyric CH2 CHzCHgNHz Valerie CHzCHzCHzNHc Isovaleric CHQOHZCHZNHQ Trimethyl Acetic. l CH2CH2CH2NH2 Pelargonic CHzCHzCHzNHz Laurie CHzCHzCHzNHz Stearic OHzCHzCHzNHz Arachirlic CHzCHzCHaNHz Eucosane-carboxylic. CH2CH2CH2NH2 Cerotic CH2CH2CH2NH2 Melissic CH2CH2CH2NH: Phenylstearic'. CHzCHzCHzNHz Benzoic CH2CHOH2NH2 Salicylic- CH2CH2CH2NH2 Cresotinim--. OH2CH2CHZNH2 P-Hydroxybenzoic CHnCH2CH2NH2 P-tert-Butylbenzoic OH2CH2CH2NH2 2-Hydroxy-3-rnethoxy benzoic- CHzCHzOHzNHz Oleic GHzCHzCHcNH? Undecylenic. CH2CH2CH2NH2 Linoleic CH2CH2CH2NH2 Hydroxybutyrrc. CHzCHzCHzNHz Methyloctadecanoic CHzCHzCHaNHz Division C The procedure employed in the manufacture of substituted imidazolines from dicarboxy acids, is comparable to that employed when monocarboxy acids are used as reactants. As in the case of the monocarboxy acids, the acid may introduce a radical having less than 8 uninterrupted carbon atoms or 8 or more uninterrupted carbon atoms.

Suitable products derived from the three amines previously noted are described in Table 3, following:

TABLE 3 RN N N N-R L Q V Ex. HOC-R-OOOH R No. Source of-CRO- 7 Malom'c CH2CHzNH Adipic CHZCHZNH Suberic CHzCHzNH Sebacic OHzCHgNH Nonodecane di- CHECHQNH carboxylic. 6c. Diglyc lic CHzCHzNH 7c.. Ethylene bis CHQOHZNH (glycuic). 8c. Methylene di- CHzCHzNH salicylic. 9c Steary1Malonic CHzCHzNH 10c- Phtialic OHZCEZNH 11c. Succinicv CH2CH2NHOH2OH2NH 12c. Gluturc. GHZCHgNHCHgCHzNH 13c Pirnelic. CHZCHZNHCHECHQNH 14c AZelftiC CH2CH2NHCHzCHzNH 15c. Eilgrsane dlca CHgCHgNHCHZCHzNE x 10. 160..-. Dilin"leie OH2OH2NHCH2CHZNH} 17c. Ismn thalic OHXCEgNHCHQCHzNH 18c- Diglyc lic CH2CHzNHCH2CH2NH 19c. Lauryl Mel nie"- CH2C H2NHCH2CH2NH 20c- Meliiiyllene di- CHZC HQNHOHECHZNH sa my 10. 21c- Malnic OH20HZNHCzHzCHzNHCHzCHzNHg 22c. Succinic. OHaCHzNHCzHgCHzNHC HZOHQNHZ 23c. Suberic. OHECH2NHC2H1CH2NHOH2CH2NH2 24c- Pirnelic CH2CH2NHC2H2OH2NHOHECHZNH; 25L Nonndecan CHZCHENHC2H2OH2NHCH2OHzNH:

carboxylic. 26c Diglyc lic CH2OHaNHCzHzCHgNHCHgCHzNHz 27c. Metihyliene di- CH2CHZNHCQH2CH2NHCH2CH2NH2 sa my 10. 28L Stearyl mal m'c. C H26 HzNHCzHzC H2NHCH2CH2NHZ 29c- Stearyl cucciuic... CH2OHzNHCzHzCHzNHCHzCHzNHz 30c- Terephthalic CHzCHzNHCzHzCHzNHCEhCHzNHz Division D In the use of dicarboxy acid's, the bulk of the examples were obtained from 3,3-iminobispropylatriine." These compounds are comparable to those which appeared in Table 3, preceding.

TABLE 4 RN I l' Nfl -R \CLRIAC/ Ex. No. HOOCRCOOH R Source of -GRG Malonic CH2CH2CH2NH2 Succinic CHzCHzCHgNHz Glutaric. (DH-2C HQCHQNH: Adipic CH2C H2O HzNHa Suberic CHQCHrCHzNHz Sebac1c OHzOHzCH NH Pimehc. CH2OHZCH2NH3 Azelaic C HzCHaC HzNHa Nonodecane dicarboxylic CHzCHzCHzNH! Eicosane dicarboxylic.

Stearyl malonic. Lauryl succinic Isotetradecyl succinlc. Phthalic Isophthalic CHzCHzCHgNHz Terephthalid- CIIQCHQCHQNH:

Glutaconic CHzCHzCHzNHn l0 CHzCHzCHzNH:

PART 2 Suitable polyols having an aldehyde group which are reactive towards basic primary amines are Well known. The preferred reactant is glucose. However, a number of additional reactants which may be included are the following: apiose, arabinose, erythrose, fucose, galacto se, glyceraldehyde, mannose, rhamnose, ribose, threose, and

xylose.

PART 3 The two types of reactants previously described in Parts 1 and 2, are combined under conventional conditions to produce a Schifis Base compound. Generally the conditions require preferably a solvent in which both reactants are soluble, which allows the reaction to proceed at a lower temperature giving a lighter colored product. The reaction may be allowed to proceed in the absence of solvent, however, eliminating the necessity of solvent removal from the viscous reaction product. This necessitates longer reaction times or higher temperatures being employed.

The procedure employed in obtaining the Schiifs Base is illustrated by the following examples:

Example I e 'One mole of the imidazoline (1a, Table I) derived from formic acid was mixed with one mole of glucose. Stirring was continued overnight and the water formed removed in v acuo. A light yellow product resulted.

Example 2e One mole of the tetrahydropyrimidine (8b, Table 2) derived from lauric acid was mixed with one mole of mannose and the resulting mixture heated. Water began to form, and could be removed, as the temperature became greater than 70 C. As heating continued the reaction became more vigorous until at C. a spontaneous rise to C. was noted. The heating was discontinued and the water formed removed in v-acuo from the red brown viscous residue.

Example 3e One mole of the d-iimidazoline (60, Table 3) derived from diglycolic acid and one mole of arabinose were refluxed with a suitable quantity of methyl alcohol to ensure homogeneity for a period of three hours. The solvent and the water formed in the reaction were re,- rnoved in vacuo giving a product characterized'by the presence of a free uncombined terminal primary amino radical.

Example4e One mole of the diimidazoline (13d, Table 4) derived from methylene disalicylic acid and two moles of ribose, were refluxed with a suitable quantity of isopropyl alcohol to ensure homogeneity for a period of three hours. The solvent and the water formed in the reaction were removed in vacuo, care being taken to reduce foaming. The product formed was a brown red viscous oil.

For sake of brevity, a number of other examples are included in Table following. It will be noted in these examples, 1e to 20c, there are included a variety of compounds, some of which include a high molal radical, and some of which do not. In some instances the compounds contain a single heterocyclic ring and in some instances two heterocyclic rings. In some instances the rings are five-membered and in other instances six-membered. Some examples are characterized by the presence of a free readily convert the Schiffs Base into suitable amines which have certain advantages in instances over the Schiifs Base in that they have greater stability. It should be pointed out that when such reactants as described in Part 1, preceding, are subjected to hydrogenation if derived from an unsaturated fatty acid or unsaturated dicarboxy acid, the conversion to the corresponding saturated compound takes place almost without exception. Thus, the hydrogenated derivatives referred to in the appended claims include not only those in which the Schiifs Base has been converted into the corresponding amine but also those in which any unsaturated groups derived from mono or dicarboxy acids have been converted into the corresponding saturated compound as noted above.

As a specific example illustrating the hydrogenation of the Schilfs Base obtained as previously described in Part 3, reference is made to the following three examples and uncombined terminal primary ammo radical. Table 6, followlng. It will be noted the procedure em- TABLE 5 Cyclic Aldehydle Molal Temp, Time, Ex. N0. Cmpd. Moles Compound Moles Ratio Solvent 0. Hours Used Employed 1 Glucose 1 l: 20 16 1 Maunose 1 1: 110 10 min. 1 l 1: 3 1 2 l: 83 3 1 1 1: 65 3 1 1 l: 65 3 1 1 1: 65 3 1 1 1: 65 3 1 1 1:1 83 3 1 1 1:1 83 3 1 1 1:1 83 3 1 1 1:1 83 3 1 1 1:1 65 3 1 2 1:2 65 3 1 2 1:2 65 3 1 2 1 :2 Isopropanol- 83 3 1 1 1:1 Methanol.-. 65 3 1 2 1:2 d0 65 3 1 1 1:1 Isoprop anol- 83 3 1 2 1:2 do 83 3 The above reaction is obtained by use of a hydroxylated aldehyde as specified. There are available a number of polyhydroxylated ketones such as dihydroxyacetone, erythrulose, fructose, sor-bose, lactulose, and mannoheptulose, which may be used in the formation of Schiifs Bases. A ketone can be used to give a somewhat com PART 4 A variety of primary amines have been combined with glucose or the like to produce a compound comparable to the one herein described in that it is a Schiifs Base. Such compounds have been described in various patents such as: I

U. S. Patent No. 1,985,424, dated December 25, 1934,

to 'Piggott V U. S. Patent No. 2,016,962, dated October 8, 1935, to

Flint et al.

U. S. Patent No. 2,016,963, dated October 8, 1935,

to Flint et al.

U. S. Patent No. 2,193,433, dated March 12, 1940, to

Salzberg Using the same hydrogenation procedure in regard to the compounds described in Part 3, preceding, one can v syrup.

ployed is substantially the one described in United States 'patents preceding.

Example 1 100 grams of the Schiffs Base (EX. 6e, Table 5) derived from glucose, triethylene tetramine, and salicyclic. acid dissolved in 500 grams of water, and ,10 gramsbf reduced nickel catalyst, containing 20% nickel supported 0 on kieselguhr, was violently agitated under 2000 pounds hydrogen pressure at a temperature of for 50 minutes. The catalyst was removed by filtration and the mother liquor concentrated, giving the reduced .Schitfs Base as a viscous non-crystalline syrup,

Example 2 grams of the Schiffs Base (Ex..11e, Table 51 derived from mannose, 3.3-iminobispropylamine and 2- V hydroxy-3-methoxybenzoic acid dissolved in'700 grams of water and-10 grams of nickel catalyst'was violently agitated under 2000 pounds hydrogen pressure at a temperature of 100 for 30 minutes. The catalyst was removed by filtration and the mother liquor concentrated, giving the product as a viscous non-crystalline Example 3] 100 grams of the Schiffs Base (Ex. 156, Table s derivedfrom glucose, tetraethylenepentamine, and succinic acid dissolved in 500 grams of alcohol, and 10 grams of Raney nickel catalyst, was violently agitated under 100 pounds of hydrogen pressure at a temperature of 50 C., for 30 minutes. The catalyst was removed by filtration and the mother liquor concentrated, care being taken to reduce foaming, giving the reduced 9 diimidazoline Schiffs Base as a viscous non-crystalline y up- TABLE 6 Crnpd. Pres., Ex Hydro- Grains Catalyst Temp., lbs. Time, No. gen- 0. Sq. In Mins.

ated

1f..- 6e--- 100 Supported Nickel. 100 2, 000 50 2f--- 1142--.. 100 do 100 2,000 30 3f 15e 100 Bailey Nickel 50 100 30 4f 1e 100 Supported Nickel. 90 2,000 30 51'..." 2e (1 110 2,000 30 6f 4e. 90 2, 000 30 7f 9:"... 25 115 2, 000 60 BI"... 148-.-. 25 .-.--d 100 2,000 60 9f.--" 17e 25 Raney Nickel. 50 100 30 1011... 20s--.. 100 Supported Nickel. 100 2, 000 60 The products described in Parts 3 and 4 may vary widely in regard to surface-active properties and particularly as far as solubility in water, or similar polar solvents go on the one hand and hydrocarbons, oils, or non-polar solvents on the other hand. A number of the products described and, in fact, all of them either before or after hydrogenation, have present one or more basic nitrogen atoms per molecule. Thus, they may be employed in the various forms in which comparable nitrogenous compounds are used, i. e., in the form of the anhydrous base, or in the form of the hydrated base (combination with water) or in the form of a salt. The salt may be a combination with an organic acid or an inorganic acid such as hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, etc., when derived from organic acids. The acid employed may be a carboxy acid or sulfonic acid. Furthermore, the acid may have more than one carboxyl group as in the case of diglycolic acid, tetracarboxybutane, etc.

When a salt is formed from a low molal organic acid, particularly a hydroxylated acid such as acetic acid, butyric acid, lactic acid, hydroxyacetic acid, gluconic acid, etc., the tendency is to increase the hydrophile properties. However, when a salt is derived from an organic acid having 8 or more carbon atoms, such as a higher fatty acid, naphthenic acid, abietic acid, or the like, the tendency is to decrease the hydrophile properties and increase the hydrophobe properties.

Any reference to the use of these acylation derivatives, as for example in the claims, specifically includes all the various forms including the salt form and the hydrated base form referred to above.

PART

In light of what has been said previously, it is obvious that the products as such and their salts, represent'complete variation in hydrophobe-hydrophile balance from products which are extremely water-soluble to products which are essentially oil-soluble and have comparatively moderate hydrophile properties.

These products or compounds may be used for various purposes in the oil industry in which other cyclic amidines or cyclic amidine derivatives have been employed. Such uses include, among others, the following: Resolution of water-in-oil emulsions; resolution of oil-in-water emulsions, prevention of corrosion particularly of ferrous equipment; use in the acidization of calcareous structures; use in secondary oil recovery, etc.

As to the use of the herein described products in the same way that conventional demulsifying agents are employed, reference is made to U. S. Patent No. 2,626,929, dated January 27, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and eifect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 72, herein described.

The new products herein described are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wet ting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

So far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the water-in-oil type, and also for that matter for numerous other purposes where surface-active materials are effective, and particularly for those uses specified elsewhere herein, it is preferred to employ oxyalkylated derivatives which are obtained by the use of monoepoxides, in such manner that the derivatives so obtained have sufiicient hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent such test for einulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

The materials herein described, in many instances have a number of uses in the petroleum industry somewhat different from those previously described.

In the first place the material is valuable as a fuel oil additive in the manner described in U. S. Patent No. 2,553,183, dated May 15, 1951, to Caron et al. It can be used in substantially the same proportions or lower proportions and this is particularly true when used in conjunction with a glyoxalidine or amido glyoxyalidine.

An analogous use in which these products are equally satisfactory, is that described in U. S. Patent No. 2,665,978, dated January 12, 1954, to Stayner et al. The amount employed is in the same proportion or lesser amounts than referred to in said aforementioned Caron et al patent.

The second use is for the purpose of inhibiting fogs in hydrocarbon products as described in U. S. Patents Nos. 2,550,981 and 2,550,982, both dated May 1, 1951, and both to Eberz. Here, again, it can be used in the same proportions as herein indicated or even small proportions.

A third use is to replace oil soluble petroleum sulfonates, so-called mahogany soaps, in the preparation of certain emulsions or soluble oils or emulsifiable lubricants where such mahogany soaps are employed. The cogeneric mixtures having this peculiar property, serve to replace all or a substantial part of the mahogany soap.

Another use is where the product does not serve as an emulsifying agent alone but serves as an adjunct.

Briefly stated, the fourth use is concerned with use as a coupling agent to be employed with an emulsifying agent. See The Composition and Structure of Technical Emulsions, J. H. Goodey, Roy. Australian Chem. Inst. J. & Proc., vol. 16, 1949, pp. 47-75. As stated, in the summary of this article, states:

The technical oil-in-water emulsion is regarded as a system of four components; the dispersion medium, consisting of the highly polar substance Water; the disperse phase composed of hydrocarbons or other substances of comparatively weak polarity; the coupling agent, being an oil-soluble substance involving an hydroxyl, carboxyl or similar polar group; and the emulsifying agent, which is a wateresoluble substance involving an hydrocarbon radical attached to an ioni'zable group.

Thus, these peculiar products, giving curdy precipitates with water, are unusually effective as coupling agents in many instances.

Fifth, these materials have particular utility in increas ing the yield of an oil well by various procedures which in essence involve the use of fracturing of the strata by means of liquid pressure. A mixture of these products with oil or oil in combination with a gel former alone,

or a gel former and finely divided mineral particles, yields a product which, when it reaches crevices in the strata which are yielding water, form a gelatinous mass of curdy precipitate or solid or semi-solid emulsion of a high viscosity. In any event, it represents a rapid gelling agent for the strata crevices and permits pressure to be applied to fracture the strata without loss of fluid through crevices, openings or the like.

The herein described products and the derivatives thereof, are particularly valuable in flooding processes for recovery of oil from subterranean oil-bearing strata when employed in the manner described in U. S. Patent No. 2,233,381, dated February 25, 1941, to De Groote and Keiser.

The application of imidazolines as sold in the open market has been suggested for a variety of industries, such as the following:

Agriculture: kerosene, phenothiazine, pyrethrum sprays, fungicides, herbicidal oils.

Anti-static treatment: for hotel rugs, hospital floors, automobile upholstery, plastic and wax polishes, wool oils, lubricants for synthetic fibers.

Building materials: water repellent treatment for plaster, concrete, cement, roofing materials, air entrainment, floor sealers, linoleum.

Cosmetics: formulation of anti-perspirants, deodorants, sun screens, hair preparations.

De-emulsifying: in antibiotic extraction, breaking crude oil and Water-gas for emulsions.

V etergents: metal cleaning emulsions, lens cleaners, floor oils, dry cleaning detergents, radiator flushes, cesspool acid, boiler scale solvents, germicidal corrosioninhibited acid detergents for dairies, enamel equipment, toilet bowls.

Leather: flat liquoring oils, pickling, acid degreasing, dye fixative.

Metals: rust preventive oils, cutting oils, water displacing compounds, pickling inhibitor, solvent degreasmg.

Paints: for improved adhesion of primers, preventing water spotting in lacquers, anti-skinning, pigment flushing, grinding and dispersing, anti-feathering in inks.

Petroleum: corrosion inhibitor and germicide in flood water treatment, de-emulsifying fuel oil additives, antistrip agent in asphalt emulsions and cutbacks.

Textiles: in rubberizing, textile oils, dyeing assistants, softening agents.

Miscellaneous: bentonite-amine complexes, metalamine complexes, preparation of pentachlorphenates, quaternaries, plastisols, and rodent repellents.

This new sub-genus of the broad class of cyclic amidines, is also effective for these same uses, part of which have been referred to previously.

PART 6 The products herein described may be combined with a variety of reactants as chemical intermediates, for instance, with various diepoxides or polyepoxides. They may be combined with a number of other monoepoxides, such as epichlorohydrin, styrene oxide, glycide and methylglycide. They may be reacted with alkyl glycidyl ether, glycidyl isopropyl ether, and glycidyl phenyl ether.

Furthermore, such products may be reacted with alkylene imines, such as ethylene imine'or propylene imine, to produce cation-active materials. Instead of an imine, one may employ What is a somewhat equivalent material, to wit a dialkylaminoexpoxypropane of the structure I I Q 7 I! wherein R and R" are alkyl groups.

The products may be combined with carboxy acids such as higher fatty acids so as to change their characteristics or with polycarboxy acids, such as diglycolic, maleic acid, phthalic acid, succinic acid, and the like, to give resins, soft polymers, or fractional esters which are essentially monomeric. Such products and others herein described, may all be used for the resolution of petroleum emulsions of the water-in-oil type. The products without further reaction are particularly valuable as additives for lubrieating oils which are derived from sources other than petroleum.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent, is:

1. A chemical compound of the structure:

in which R is the carboxyl-free residue of an acid having not over 2 carboxyl radicals; R1 and R are selected from the class consisting of:

v in which is the carboxyl-free residue of an acid 13 not over 2 carboxyl radicals; R1 and R are selected from the class consisting of CH: -CH2(!JHCH:-

H H HCH HCH R2(OH)n' is the aldehyde oxygen-free residue of a 3 to 6 carbon atom containing polyol having an aldehyde radical and reactive to primary amines; R3 is selected from the class consisting of Hz and R2(OI-l)1u; n is a small whole number including zero; n is a small whole number greater than one but not greater than five; and n" is a numeral not greater than one and including zero.

3. A chemical compound as defined in claim 2 with the proviso that R1 and R is the ethylene radical.

4. A chemical compound as defined in claim 2 with the proviso that R1 and R is the ethylene radical and n" is zero.

5. A chemical compound as defined in claim 2 with the proviso that R1 and R is the ethylene radical, n" is zero, and n is at least one and not greater than 2.

6. A chemical compound as defined in claim 2 with the proviso that R1 and R is the ethylene radical, n" is zero, n is at least one and not greater than 2, and with the further proviso that the radical RC/ is derived from a detergent-forming acid having at least 8 carbon atoms and not over 30 carbon atoms.

7. A chemical compound as defined in claim 2 with the proviso that R1 and R is the ethylene radial, n is zero, 21 is at least one and not greater than 2, with the further proviso that the radical is the residue of a higher fatty acid having at least 8 carbon atoms and not over 22 carbon atoms.

8. A chemical compound as defined in claim 2 with the proviso that R1 and R is the ethylene radical, n" is zero, n is at least one and not greater than 2, Wtih the further proviso that the radical is the residue of a higher fatty acid having at least 8 carhon atoms and not over 22 carbon atoms in which Rz(OH)1u is a glucose residue.

9. A chemical compound as defined in claim 2 with the proviso that R1 and R is the ethylene radical, n" is zero, It is at least one and greater than 2, with the further proviso that the radical is the residue of a higher fatty acid having at least 10 carbon atoms and not over 20 carbon atoms in which R2(0H)n' is a glucose residue.

10. A chemical compound as defined in claim 2 with the proviso that R1 and R is the ethylene radical, n" is zero, n is at least one and greater than 2, with the further proviso that the radical is the residue of a higher fatty acid having at least 12 carbon atoms and not over 18 carbon atoms in which R2(OH)11.' is a glucose residue.

References Cited in the file of this patent UNITED STATES PATENTS 2,016,963 Flint et a1 Oct. 8, 1935 2,193,433 Salzberg Mar. 2, 1940 2,713,583 Smith July 19, 1955 OTHER REFERENCES Fiescr and Fieser: Organic Chemistry, published by D. C. Heath and Company (Boston), 1950 (pages 371 and 638). 

1. A CHEMICAL COMPOUND OF THE STRUCTURE: 